EP0041214A1 - Process for the preparation of polar-modified polypropylene, and it use - Google Patents

Process for the preparation of polar-modified polypropylene, and it use Download PDF

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Publication number
EP0041214A1
EP0041214A1 EP81103999A EP81103999A EP0041214A1 EP 0041214 A1 EP0041214 A1 EP 0041214A1 EP 81103999 A EP81103999 A EP 81103999A EP 81103999 A EP81103999 A EP 81103999A EP 0041214 A1 EP0041214 A1 EP 0041214A1
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Prior art keywords
polypropylene
weight
parts
monomer
meth
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German (de)
French (fr)
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Ulrich Dr. Grigo
Josef Dr. Merten
Rudolf Dr. Binsack
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the invention relates to a process for producing polar-modified polypropylene by polymerizing polar vinyl monomers on or in the surface of polypropylene particles swollen with organic solvents, and to the use thereof.
  • One way to modify polypropylene is to graft polymerize suitable monomers in the presence of polypropylene under the influence of high energy radiation.
  • These methods e.g. described in US Pat. Nos. 3,290,415 and 3,347,692 are, in part, very effective, but have no technical significance because they require special devices for graft polymerization under irradiation, which is an economic and technical problem.
  • the polymerization can only be carried out in a dilute solution.
  • the process has the disadvantage that only relatively low degrees of grafting are achieved.
  • the polypropylene particles are only impregnated with monomers such as styrene and styrene derivatives.
  • Polar monomers such as acrylates, acrylonitrile, acrylamide and maleic anhydride do not swell polypropylene. They are therefore used in a mixture with a swellable monomer such as styrene, styrene in the mixture having to be in a large excess in order to achieve swelling of the polypropylene.
  • This process has the disadvantage that polar monomers can only be grafted onto polypropylene together with an excess of non-polar monomers, which leads to mixed graft polymers which contain relatively little polar graft monomer.
  • the object of the present invention was now to produce homogeneous polypropylene graft polymers which contain units of only polar monomers grafted on.
  • the object was achieved in that - starting from the process of DE-OS 2 640 059 - the swelling of the polypropylene is carried out with a suitable organic solvent containing the polar monomers.
  • the polar monomers can penetrate into the swollen polypropylene and allow relatively high degrees of grafting with the polar monomers.
  • the polar monomers are 10-1200, preferably 20-500 parts by weight. of organic solvents used.
  • polypropylene means crystalline homopolypropylene and crystalline copolymers of copolymerized units of at least 70% by weight of propylene and another ⁇ -olefin, preferably ethylene.
  • the polypropylene particles should preferably be in the form of a powder with an average particle size of 10-2000 nm and with a specific surface area of 0.1-10 m 2 / g in order to quickly and completely impregnate the polypropylene particles with the solvent or monomers to reach.
  • the process according to the invention is for the graft polymerization of polar vinyl monomers such as C 1 -C 7 -alkyl acrylate ten, C 1 -C 7 alkyl methacrylates, acrylonitrile, acrylamide, acrylic acid, methacrylic acid, glycidyl (meth) acrylate, ⁇ - (meth) acryloyloxy propyl trimethoxy silane and / or maleic anhydride on polypropylene are suitable.
  • Vinyl monomers such as acrylic acid, glycidyl methacrylate and ⁇ -methacrloyloxypropyltrimethoxysilane have proven to be particularly suitable.
  • the vinyl monomer is generally used in an amount between about 4-30 parts by weight according to the invention. to 100 parts by weight of the propylene polymer used. For quantities over 30 parts by weight only a part of the monomer is able to penetrate into the polypropylene, so that in the course of the polymerization, in addition to the graft copolymer, a relatively large proportion of homopolymer is formed from the vinyl monomer. As the proportion of homopolymer in the graft copolymer increases, the homogeneity of the particles decreases. For quantities below 4 parts by weight. Vinyl monomers have practically no influence on the properties of the graft copolymer.
  • the polymerization initiator used in the process according to the invention is said to be soluble in the organic solvent and in the graft monomer, but insoluble in water, since the polymerization is carried out in aqueous suspension.
  • the decomposition temperature of the polymerization initiator used should be about 85-135 ° C. for a half-life of 2 hours. If the initiator used has a decomposition temperature lower than 80 ° C, the polymerization takes place in the The swelling or impregnation takes place so that no homogeneous graft copolymer is obtained.
  • Typical examples of polymerization initiators which are suitable for the process of the invention are dibenzoyl peroxide, tert-butyl-2-ethylhexoate, t-Butylperoxidiethylacetat and tert-butyl peroxy-isobut y rat.
  • the polymerization initiator is generally used in an amount of about 0.1 to 10 parts by weight. to 100 parts by weight Vinyl monomer used. If the amount is less than 0.1% by weight, the vinyl monomer is not completely polymerized. If the amount is greater than about 10 parts by weight, there is a risk that residues of undecomposed polymerization initiator remain in the graft copolymer, which have an adverse effect on the processing behavior of the graft copolymer. In order to achieve the most complete possible decomposition of the polymerization initiator, the polymerization duration should be at least five half-lives of the polymerization initiator.
  • the aqueous suspension is prepared by first mixing the polypropylene powder homogeneously with the appropriate amount of solvent, monomer and polymerization initiator. This mixture is stirred into water into which a suspending agent such as e.g. Polyvinyl alcohol or methyl cellulose was dissolved in the usual amount.
  • a suspending agent such as e.g. Polyvinyl alcohol or methyl cellulose was dissolved in the usual amount.
  • the concentration of the polypropylene particles in the aqueous suspension is not particularly limited, provided that the system can be easily stirred.
  • the suspension usually contains 100 to 2000 parts by weight per 100 parts by weight of polypropylene. Water, preferably 20 to 1000 parts by weight.
  • the aqueous suspension is first stirred for several hours at a temperature below the decomposition temperature of the polymerization initiator, preferably at 40 to 85 ° C.
  • the polypropylene particles are swollen by the organic solvent, which means that the vinyl monomer together with the polymerization initiator can penetrate into the polypropylene.
  • the polymerization is then carried out at a temperature of 85 ° C to 150 ° C. At temperatures up to 100 ° C the polymerization can be carried out at normal pressure, at temperatures above 100 ° C it must be carried out under pressure.
  • the temperature need not be constant in the course of the polymerization, but rather. can also vary or increase gradually.
  • the shape of the polypropylene particles and the viscosity of the suspension remain practically unchanged during the polymerization.
  • the polymerization mixture obtained is cooled after the polymerization and then further treated in the same manner as in the case of the usual polymerization in aqueous suspension.
  • the copolymer prepared according to the invention is characterized in that in the Polypropylene graft copolymer made from almost spherical particles, the graft branches not only on the particle surface, but also - due to the swelling - in the polypropylene particles.
  • the pclar-modified polypropylene particles are particularly suitable as an additive (approx. 1 to 50 wt.%, Preferably 3 to 20 wt Filler or glass fiber and matrix is achieved.
  • Polypropylene compounds modified in this way have a significantly higher flexural strength and impact resistance than unmodified polypropylene compounds.
  • additions of polar-modified polypropylene to unmodified polypropylene result in better paintability and printability. Additions of polar-modified polypropylene improve blends of polypropylene with polar rubbers such as ethylene-vinyl acetate copolymers, acrylate rubbers, acrylonitrile-butadiene rubbers and others. coupling polypropylene / rubber.
  • PP polypropylene
  • Example 2 As in Example 1, but instead of 10 parts of n-butyl acrylate and 30 parts of chlorobenzene, 2 parts of methacrylic acid and 10 parts of chlorobenzene are used. Degree of grafting 19%.
  • Table 1 lists polypropylene graft copolymers which were prepared in the absence or in the presence of a swelling solvent, in accordance with the conditions of Example 1.
  • the graft copolymers prepared in the presence of chlorobenzene as swelling solvents always have higher degrees of grafting than corresponding graft polymers which are prepared without swelling solvents were.
  • graft copolymers are also listed which, according to DE-OS 2 640 059, contain styrene as Swelling agents have been produced. They have markedly lower degrees of grafting than those made with chlorobenzene.
  • the degrees of grafting were determined by heating the polypropylene graft copolymer one percent in xylene under reflux for half an hour. The hot solution is then added to the same amount of cold ethyl acetate with stirring. The mixture obtained is left to stand at room temperature for one day, during which the polypropylene graft copolymer precipitates. The precipitated product is filtered off, dried and examined for undissolved graft components (IR spectrum, oxygen analysis). The degree of grafting is defined as the ratio of the proportion of grafting monomer remaining on the polypropylene after the repeating to that determined before the repeating.
  • Table 2 shows selected mechanical properties of glass fiber reinforced polypropylene compounds.
  • the compounds grafted with acrylic acid PP have a significantly higher property level than a compound with ungrafted polypropylene (compounds 2 and 3 compared to compound 1). However, if you compare Compounds 2 and 3 with each other, both 10 parts.
  • Compound 3 Containing acrylic acid-grafted polypropylene, Compound 3 has a much higher strength and Impact Strength as Compound 2.
  • Compound 3 contains an acrylic acid-grafted polypropylene that has been grafted with an addition of organic solvent, while Compound 2 contains acrylic acid-grafted polypropylene that has been grafted without the addition of an organic solvent.
  • the polypropylene used for compound 2 (comparative example) and grafted without the addition of an organic solvent corresponds to the graft copolymer of test 3 from table 1 and the polypropylene used for compound 3 (example according to the invention), grafted in the presence of chlorobenzene, corresponds to the graft copolymer of test 4 from table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Wäßrige Suspensionen von Polypropylen oder Propylen-Ethylen-Copolymerisaten werden mit einem organischen Lösungsmittel (Kp760:>= 100°C), das in der Lage ist, das Propylenpolymerisat anzuquellen, verrührt. Anschließend wird das gequollene Propylenpolymerisat (100 Gew.-Teile) mit 4 - 30 Gew.-Teilen eines polaren Monomeren in Gegenwart eines Radikale bildenden Initiators bei >= 85°C pfropfpolymerisiert. Polare Monomere sind C1-C7-(Meth)Acrylsäurealkylester, (Meth)Acrylsäure, Acrylnitril, Acrylamid, Glycidyl(meth)acrylat, Maleinsäureanhydrid, γ-(Meth)Acryloyloxy-propyl-trimethoxy-silan und andere. Das Pfropfpolymerisat wird zur Verbesserung der mechanischen Eigenschaften nicht-modifiziertem, gegebenenfalls glasfaserverstärktem Polypropylen zugesetzt.Aqueous suspensions of polypropylene or propylene-ethylene copolymers are stirred with an organic solvent (bp760:> = 100 ° C) which is able to swell the propylene polymer. The swollen propylene polymer (100 parts by weight) is then graft-polymerized with 4-30 parts by weight of a polar monomer in the presence of a free radical initiator at> = 85 ° C. Polar monomers are C1-C7- (meth) acrylic acid alkyl esters, (meth) acrylic acid, acrylonitrile, acrylamide, glycidyl (meth) acrylate, maleic anhydride, γ- (meth) acryloyloxy-propyl-trimethoxy-silane and others. To improve the mechanical properties, the graft polymer is added to unmodified, optionally glass-fiber-reinforced polypropylene.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von polarmodifiziertem Polypropylen durch Polymerisation von polaren Vinylmonomeren an bzw. in der Oberfläche von mit organischen Lösungsmitteln angequollenen Polypropylen- teilchen, sowie seine Verwendung.The invention relates to a process for producing polar-modified polypropylene by polymerizing polar vinyl monomers on or in the surface of polypropylene particles swollen with organic solvents, and to the use thereof.

Zur Erhöhung von mechanischen Eigenschaften wie Steifigkeit, Biegefestigkeit, Zugfestigkeit, Schlagzähigkeit, Dimensionsstabilität und anderer Eigenschaften von Glasfaser-verstärktem bzw. gefülltem Polypropylen ist es notwendig, zumindest einen Teil des Polypropylens so zu modifizieren, daß eine verbesserte Haftung zwischen Verstärkungsmaterial und Matrix erreicht wird.To increase mechanical properties such as rigidity, bending strength, tensile strength, impact strength, dimensional stability and other properties of glass fiber reinforced or filled polypropylene, it is necessary to modify at least part of the polypropylene so that an improved adhesion between the reinforcing material and the matrix is achieved.

Ein Weg, Polypropylen zu modifizieren, ist die Pfropfpolymerisation von geeigneten Monomeren in Gegenwart von Polypropylen unter dem Einfluß von energiereicher Strahlung. Diese Verfahren, die z.B. in den Patentschriften US-PS 3 290 415 und US-PS 3 347 692 beschrieben werden, sind z.T. sehr wirksam, haben jedoch keine technische Bedeutung erlangt, weil sie besondere Vorrichtungen für die Pfropfpolymerisation unter Bestrahlung voraussetzen, was ein wirtschaftliches und technisches Problem darstellt.One way to modify polypropylene is to graft polymerize suitable monomers in the presence of polypropylene under the influence of high energy radiation. These methods, e.g. described in US Pat. Nos. 3,290,415 and 3,347,692 are, in part, very effective, but have no technical significance because they require special devices for graft polymerization under irradiation, which is an economic and technical problem.

Verfahren, bei denen Polypropylen im geschmolzenen Zustand in Gegenwart von radikalischen Initiatoren gepfropft wird, sind ebenfalls bekannt (vgl. DE-OS 2 426 972 und US-PS 3 882 194). Diese Verfahren bringen jedoch die Schwierigkeiten mit sich, daß Polypropylen im geschmolzenen Zustand leicht durch einen radikalischen Angriff zu Produkten mit niedrigen Molekulargewichten abgebaut wird.Processes in which polypropylene is grafted in the molten state in the presence of radical initiators are also known (cf. DE-OS 2,426,972 and US Pat. No. 3,882,194). However, these processes have the difficulty that polypropylene in the molten state is easily degraded by radical attack to low molecular weight products.

Es ist auch bekannt, die Pfropfpolymerisation von Polypropylen in Lösung durchzuführen, wobei ein Lösungsmittel wie Xylol oder Chlorbenzol benutzt wird.It is also known to carry out the graft polymerization of polypropylene in solution using a solvent such as xylene or chlorobenzene.

Wegen der geringen Löslichkeit des Polypropylens in diesen Lösungsmitteln kann die Polymerisation nur in einer verdünnten Lösung durchgeführt werden. Das Verfahren hat den Nachteil, daß nur relativ geringe Pfropfgrade erreicht werden.Because of the low solubility of polypropylene in these solvents, the polymerization can only be carried out in a dilute solution. The process has the disadvantage that only relatively low degrees of grafting are achieved.

Weiterhin ist es aus der DE-OS 2 658 681 bekannt, VinylMonomere in einem wäßrigen Dispersionssystem in.Gegenwart von Polypropylen-Teilchen und Benetzungsmitteln zu polymerisieren. Hier neigt die Polymerisationsreaktion dazu, praktisch nur auf der Oberfläche stattzufinden, da das Polypropylen von den polaren Monomeren, z.B. Acrylamid, Acrylaten u.a. nicht angequollen wird. Dieses Verfahren erlaubt jedoch hohe Polypropylen-Konzentrationen, da die Viskosität der wäßrigen Dispersion praktisch nur vom Wasser bestimmt wird.Furthermore, it is known from DE-OS 2 658 681 to polymerize vinyl monomers in an aqueous dispersion system in the presence of polypropylene particles and wetting agents. Here the polymerization reaction tends to take place practically only on the surface, since the polypropylene is derived from the polar monomers, e.g. Acrylamide, acrylates and others is not swollen. However, this method allows high polypropylene concentrations, since the viscosity of the aqueous dispersion is determined practically only by water.

Bei einem ähnlichen Verfahren, beschrieben in DE-OS 2 640 059, werden die Polypropylen-Teilchen in wäßriger Suspension unterhalb der Zersetzungstemperatur des radikalischen Initiators mit dem Monomeren getränkt und anschließend bei höheren Temperaturen gepfropft. Als pfropfbare Monomere werden Vinylmonomere wie Styrol und Derivate, Alkyl-(meth)-acrylate, Acrylnitril, Acrylamid, Maleinsäureanhydrid sowie Mischungen von Styrol mit den aufgeführten anderen Monomeren verwendet. Durch die vorherige Tränkung der Polypropylen-Teilchen mit dem Monomeren soll der Pfropfgrad erhöht und eine nicht nur an der Oberfläche der Polypropylen-Teilchen stattfindende Pfropfpolymerisation erreicht werden. Eine Tränkung der Polypropylen-Teilchen wird jedoch nur mit Monomeren wie Styrol und Styrol-Derivaten erreicht. Polare Mononere wie Acrylate, Acrylnitril, Acrylamid und Maleinsäureanhydrid quellen Polypropylen nicht an. Sie werden deshalb im Gemisch mit einem quellfähigen Monomeren wie Styrol eingesetzt, wobei Styrol in dem Gemisch stark im Überschuß sein muß, um eine Quellung des Polypropylens zu erreichen. Dieses Verfahren hat den Nachteil, da-ß polare Monomere nur zusammen mit einem Überschuß an unpolaren Monomeren auf Polypropylen pfropfbar sind, was zu Mischpfropfpolymerisaten führt, die relativ wenig polares Pfropfmonomer enthalten.In a similar process, described in DE-OS 2 640 059, the polypropylene particles are impregnated with the monomer in aqueous suspension below the decomposition temperature of the radical initiator and then grafted at higher temperatures. Vinyl monomers such as styrene and derivatives, alkyl (meth) acrylates, acrylonitrile, acrylamide, maleic anhydride and mixtures of styrene with the other monomers listed are used as graftable monomers. The previous impregnation of the polypropylene particles with the monomer is intended to increase the degree of grafting and to achieve a graft polymerization which does not only take place on the surface of the polypropylene particles. However, the polypropylene particles are only impregnated with monomers such as styrene and styrene derivatives. Polar monomers such as acrylates, acrylonitrile, acrylamide and maleic anhydride do not swell polypropylene. They are therefore used in a mixture with a swellable monomer such as styrene, styrene in the mixture having to be in a large excess in order to achieve swelling of the polypropylene. This process has the disadvantage that polar monomers can only be grafted onto polypropylene together with an excess of non-polar monomers, which leads to mixed graft polymers which contain relatively little polar graft monomer.

Aufgabe der vorliegenden Erfindung war es nun, homogene Polypropylen-Pfropfpolymerisate herzustellen, die Einheiten von nur polaren Monomeren aufgepfropft enthalten. Die Aufgabe wurde dadurch gelöst, daß - ausgehend vom Verfahren der DE-OS 2 640 059 - das Quellen des Polypropylens mit einem dafür geeigneten organischen Lösungsmittel, das die polaren Monomeren enthält, durchgeführt wird. In das gequollene Polypropylen können die polaren Monomeren eindringen und erlauben relativ hohe Pfropfgrade mit den polaren Monomeren.The object of the present invention was now to produce homogeneous polypropylene graft polymers which contain units of only polar monomers grafted on. The object was achieved in that - starting from the process of DE-OS 2 640 059 - the swelling of the polypropylene is carried out with a suitable organic solvent containing the polar monomers. The polar monomers can penetrate into the swollen polypropylene and allow relatively high degrees of grafting with the polar monomers.

Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von modifizierten Polypropylen-Teilchen durch Polymerisation von Vinylmonomeren in wäßriger Suspension, wobei

  • a) eine wäßrige Suspension hergestellt wird, die auf 100 bis 2000 Gew.-Tle. Wasser 100 Gew.-Tle. Polypropylen-Teilchen, 4-30 Gew.-Tle eines Vinylmonomeren, und - auf 100 Gew.-Tle. des Monomeren bezogen - 0,1 - 10 Gew.-Tle. eines Radikalkettenpolymerisationsinitiators enthält, der bei einer Temperatur von 80-135°C eine Halbwertszeit von mindestens 2 h aufweist,
  • b) die wäßrige Suspension ohne Zersetzung des Initiators erwärmt wird, wobei das Polypropylen angequollen und das Monomere in das Polypropylen eindringt, und anschließend
  • c) die wäßrige Suspension so lange auf Temperaturen ≥ 85°C gehalten wird, bis die Polymerisation des Monomeren abgeschlossen ist, dadurch gekennzeichnet, daß das Vinylmonomere ein polares Vinylmonomeres ist, und die wäßrige Suspension zusätzlich 30-1200 Gew.-Tle., bezogen auf 100 Gew.-Tle. des Monomeren, eines organischen Lösungsmittels enthält, das in der Lage ist, Polypropylen anzuquellen, dessen Siedepunkt bei 760 Torr mindestens 100°C beträgt und das mit den Monomeren in beliebigen Verhältnissen mischbar ist
The invention thus relates to a process for the preparation of modified polypropylene particles by polymerizing vinyl monomers in aqueous suspension, wherein
  • a) an aqueous suspension is prepared, the 100 to 2000 parts by weight. Water 100 parts by weight Polypropylene particles, 4-30 parts by weight of a vinyl monomer, and - to 100 parts by weight. of the monomer - 0.1-10 parts by weight. a radical polymerization initiator which has a half-life of at least 2 hours at a temperature of 80-135 ° C,
  • b) the aqueous suspension is heated without decomposition of the initiator, the polypropylene swelling and the monomer penetrating into the polypropylene, and then
  • c) the aqueous suspension is kept at temperatures ≥ 85 ° C until the polymerization of the Monomers is completed, characterized in that the vinyl monomer is a polar vinyl monomer and the aqueous suspension additionally 30-1200 parts by weight, based on 100 parts by weight. of the monomer, an organic solvent which is able to swell polypropylene, whose boiling point at 760 Torr is at least 100 ° C and which is miscible with the monomers in any ratio

Das vorliegende Verfahren besitzt nicht nur den Vorteil, Polypropylen durch die Zugabe des organischen Lösungsmittels anzuquellen, wodurch ein Eindringen des polaren Monomeren in das Polypropylen ermöglicht wird, sondern es können auch nahezu beliebige Monomerkonzentrationen in sehr homogener Weise durch variable Einstellung des Monomer/Lösungsmittel-Verhältnisses auf bzw. in die Polypropylen-Teilchen gebracht werden. Voraussetzung für eine weitgehend homogene Verteilung des polaren Monomeren im Polypropylen ist, daß organische Lösungsmittel verwandt werden, die in der Lage sind, Polypropylen schon deutlich unterhalb der Zersetzungstemperatur des radikalischen Initiators anzuquellen. Weiterhin sollten die organischen Lösungsmittel völlig mischbar mit den polaren Monomeren sein. Die Siedepunkte der organischen Lösungsmittel sollten bei 760 Torr mindestens 100°C betragen, damit ein Abdestillieren während der Polymerisation möglichst unterbleibt. Andererseits sollten die Siedepunkte auch nicht zu hoch sein, um die organ. Lösungsmittel während der Trocknung der gepfropften Polypropylen-Teilchen leicht entfernen zu können.The present method not only has the advantage of swelling polypropylene by the addition of the organic solvent, which enables the polar monomer to penetrate into the polypropylene, but also almost any monomer concentrations can be obtained in a very homogeneous manner by variable adjustment of the monomer / solvent ratio placed on or in the polypropylene particles. A prerequisite for a largely homogeneous distribution of the polar monomer in polypropylene is that organic solvents are used which are able to swell polypropylene well below the decomposition temperature of the radical initiator. Furthermore, the organic solvents should be completely miscible with the polar monomers. The boiling points of the organic solvents should be at least 100 ° C at 760 Torr, so that distillation during the polymerization is avoided as far as possible. On the other hand, the boiling points should not be too high to To be able to easily remove solvents during the drying of the grafted polypropylene particles.

Als Lösungsmittel kommen in Betracht: aromatische Kohlenwasserstoffe, aliphatische Kohlenwasserstoffe und halogenierte aromatische Kohlenwasserstoffe sowie deren Mischungen mit einem Siedepunkt bei 760 Torr von 100°C bis 250°C, vorzugsweise 110°C bis 160°C. Namentlich seien beispielsweise genannt: Toluol, Xylol, Chlorbenzol, Dichlorbenzol, Cyclohexanon, Diethylenglykoldiethylether, Di-n-butylether.Suitable solvents are: aromatic hydrocarbons, aliphatic hydrocarbons and halogenated aromatic hydrocarbons and mixtures thereof with a boiling point at 760 Torr from 100 ° C. to 250 ° C., preferably 110 ° C. to 160 ° C. Examples include: toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexanone, diethylene glycol diethyl ether, di-n-butyl ether.

Vorzugsweise werden Toluol, Xylol, Chlorbenzol und Dichlorbenzol eingesetzt.Toluene, xylene, chlorobenzene and dichlorobenzene are preferably used.

Bezogen auf 100 Gew.-Tle. der polaren Monomeren werden 10-1200, vorzugsweise 20-500 Gew.-Tle. der organischen Lösungsmittel eingesetzt.Based on 100 parts by weight. the polar monomers are 10-1200, preferably 20-500 parts by weight. of organic solvents used.

Unter Polypropylen wird in dieser Anmeldung kristallines Homopolypropylen sowie kristalline Copolymere aus copolymerisierten Einheiten von mindestens 70 Gew.-% Propylen und einem anderen α-Olefin, vorzugsweise Ethylen verstamden. Die Polypropylenteilchen sollten vorzugsweise in Form eines Pulvers mit einer mittleren Teilchengröße von 10-2000 nm und mit einer spezifischen Oberfläche von 0,1-10 m2/g vorliegen, um eine schnelle und vollständige Tränkung der Polypropylen-Teilchen mit dem Lösungsmittel bzw. Monomeren zu erreichen.In this application, polypropylene means crystalline homopolypropylene and crystalline copolymers of copolymerized units of at least 70% by weight of propylene and another α-olefin, preferably ethylene. The polypropylene particles should preferably be in the form of a powder with an average particle size of 10-2000 nm and with a specific surface area of 0.1-10 m 2 / g in order to quickly and completely impregnate the polypropylene particles with the solvent or monomers to reach.

Das erfindungsgemäße Verfahren ist für die Pfropfpolymerisation von polaren Vinylmonomeren wie C1-C7-Alkylacrylaten, C1-C7-Alkylmethacrylaten, Acrylnitril, Acrylamid, Acrylsäure, Methacrylsäure, Glycidyl(meth)acrylat, δ-(Meth)Acryloyloxy-propyl- trimethoxy-silan und/oder Maleinsäureanhydrid auf Polypropylen geeignet. Als besonders geeignet haben sich Vinylmonomere wie Acrylsäure, Glycidylmethacrylat und δ-Methacrloyloxy-propyl-trimethoxysilan erwiesen.The process according to the invention is for the graft polymerization of polar vinyl monomers such as C 1 -C 7 -alkyl acrylate ten, C 1 -C 7 alkyl methacrylates, acrylonitrile, acrylamide, acrylic acid, methacrylic acid, glycidyl (meth) acrylate, δ- (meth) acryloyloxy propyl trimethoxy silane and / or maleic anhydride on polypropylene are suitable. Vinyl monomers such as acrylic acid, glycidyl methacrylate and δ-methacrloyloxypropyltrimethoxysilane have proven to be particularly suitable.

Das Vinylmonomere wird nach der Erfindung im allgemeinen in einer Menge zwischen etwa 4-30 Gew.-Tln. auf 100 Gew.-Tle. des Propylen-Polymeren eingesetzt. Bei Mengen über 30 Gew.-Tle. vermag nur noch ein Teil des Monomeren in das Polypropylen einzudringen, so daß im Verlauf der Polymerisation neben Pfropfcopolymerisat auch ein relativ großer Anteil Homopolymerisat aus dem Vinylmonomeren entsteht. Mit steigendem Anteil an Homopolymerisat im Pfropfcopolymerisat nimmt die Homogenität der Teilchen ab. Bei Mengen unter 4 Gew.-Tln. Vinylmonomeren werden die Eigenschaften des Pfropfcopolymerisats praktisch noch nicht beeinflußt.The vinyl monomer is generally used in an amount between about 4-30 parts by weight according to the invention. to 100 parts by weight of the propylene polymer used. For quantities over 30 parts by weight only a part of the monomer is able to penetrate into the polypropylene, so that in the course of the polymerization, in addition to the graft copolymer, a relatively large proportion of homopolymer is formed from the vinyl monomer. As the proportion of homopolymer in the graft copolymer increases, the homogeneity of the particles decreases. For quantities below 4 parts by weight. Vinyl monomers have practically no influence on the properties of the graft copolymer.

Der in dem Verfahren nach der Erfindung verwendete Polymerisationsinitiator soll in dem organischen Lösungsmittel und in dem Pfropfmonomeren löslich, in Wasser dagegen unlöslich sein, da die Polymerisation in wäßriger Suspension durchgeführt wird.The polymerization initiator used in the process according to the invention is said to be soluble in the organic solvent and in the graft monomer, but insoluble in water, since the polymerization is carried out in aqueous suspension.

Sinnvollerweise sollte die Zersetzungstemperatur des verwendeten Polymerisationsinitiators für eine Halbwertszeit von 2 Stunden etwa 85 -135°C betragen. Wenn der eingesetzte Initiator eine niedrigere Zersetzungstemperatur als 80°C hat, findet die Polymerisation schon im Laufe der Quellung bzw. Tränkung statt, so daß kein homogenes Pfropfcopolymerisat erhalten wird.The decomposition temperature of the polymerization initiator used should be about 85-135 ° C. for a half-life of 2 hours. If the initiator used has a decomposition temperature lower than 80 ° C, the polymerization takes place in the The swelling or impregnation takes place so that no homogeneous graft copolymer is obtained.

Typische Beispiele von Polymerisationsinitiatoren, die sich für das Verfahren der Erfindung eignen, sind Dibenzoylperoxid, tert.-Butylperoxid-2-ethylhexoat, tert.-Butylperoxidiethylacetat und tert.-Butyl-peroxi- isobutyrat.Typical examples of polymerization initiators which are suitable for the process of the invention are dibenzoyl peroxide, tert-butyl-2-ethylhexoate, t-Butylperoxidiethylacetat and tert-butyl peroxy-isobut y rat.

Der Polymerisationsinitiator wird im allgemeinen in einer Menge von etwa 0,1 bis 10 Gew.-Tln. auf 100 Gew.-Tle. Vinyl-Monomeres eingesetzt. Wenn die Menge unter 0,1 Gew.-% liegt, wird das Vinylmonomere nicht vollständig polymerisiert. Ist die Menge größer als etwa 10 Gew.-Tle, so besteht die Gefahr, daß Reste unzersetzten Polymerisationsinitiators im Pfropfcopolymerisat verbleiben, die einen nachteiligen Einfluß auf das Verarbeitungsverhalten des Pfropfcopolymerisats haben. Um eine möglichst vollständige Zersetzung des Polymerisationsinitiators zu erreichen, sollte die Polymerisationsdauer mindestens fünf Halbwertszeiten des Polymerisationsinitiators betragen.The polymerization initiator is generally used in an amount of about 0.1 to 10 parts by weight. to 100 parts by weight Vinyl monomer used. If the amount is less than 0.1% by weight, the vinyl monomer is not completely polymerized. If the amount is greater than about 10 parts by weight, there is a risk that residues of undecomposed polymerization initiator remain in the graft copolymer, which have an adverse effect on the processing behavior of the graft copolymer. In order to achieve the most complete possible decomposition of the polymerization initiator, the polymerization duration should be at least five half-lives of the polymerization initiator.

Die Herstellung der wäßrigen Suspension erfolgt so, daß zunächst das Polypropylenpulver mit der entsprechenden Menge Lösungsmittel, Monomer und Polymerisationsinitiator homogen vermiscbt wird. Diese Mischung wird in Wasser eingerührt, in das ein Suspensionsmittel wie z.B. Polyvinylalkohol oder Methylcellulose in üblicher Menge gelöst wurde.The aqueous suspension is prepared by first mixing the polypropylene powder homogeneously with the appropriate amount of solvent, monomer and polymerization initiator. This mixture is stirred into water into which a suspending agent such as e.g. Polyvinyl alcohol or methyl cellulose was dissolved in the usual amount.

Die Konzentration der Polypropylen-Teilchen in der wäßrigen Suspension unterliegt keinen besonderen Beschränkungen, vorausgesetzt, daß das System leicht gerührt werden kann. Üblicherweise enthält die Suspension auf 100 Gew.-Tle Polypropylen 100 bis 2000 Gew.-Tle. Wasser, vorzugsweise 2Ö0 bis 1000 Gew.-Tle. Die wäßrige Suspension wird zunächst mehrere Stunden bei einer Temperatur unterhalb der Zersetzungstemperatur des Polymerisationsinitiators, vorzugsweise bei 40 bis 85°C gerührt. Hierbei werden die Polypropylenteilchen durch das organische Lösungsmittel angequollen, wodurch gleichzeitig das Vinylmonomere zusammen mit dem Polymerisationsinitiator in das Polypropylen eindringen kann. Anschließend wird die Polymerisation bei einer Temperatur von 85°C bis 150°C durchgeführt. Bei Temperaturen bis 100°C kann die Polymerisation bei Normaldruck, bei Temperaturen über 100°C muß sie unter Druck durchgeführt werden. Die Temperatur braucht nicht im Verlaufe der Polymerisation konstant zu sein, sondern. kann auch stufenweise variiert bzw. gesteigert wenden.The concentration of the polypropylene particles in the aqueous suspension is not particularly limited, provided that the system can be easily stirred. The suspension usually contains 100 to 2000 parts by weight per 100 parts by weight of polypropylene. Water, preferably 20 to 1000 parts by weight. The aqueous suspension is first stirred for several hours at a temperature below the decomposition temperature of the polymerization initiator, preferably at 40 to 85 ° C. Here, the polypropylene particles are swollen by the organic solvent, which means that the vinyl monomer together with the polymerization initiator can penetrate into the polypropylene. The polymerization is then carried out at a temperature of 85 ° C to 150 ° C. At temperatures up to 100 ° C the polymerization can be carried out at normal pressure, at temperatures above 100 ° C it must be carried out under pressure. The temperature need not be constant in the course of the polymerization, but rather. can also vary or increase gradually.

Die Polymerisationszeit liegt gewöhnlich im Bereich von etwa 3 bis 12 h.The polymerization time is usually in the range of about 3 to 12 hours.

Die Gestalt der Polypropylen-Teilchen sowie die Viskosität der Suspension bleiben während der Polymerisation praktisch unverändert. Die erhaltene Polymerisationsmischung wird nach der Polymerisation abgekühlt und dann im derselben Weise weiterbehandelt, wie es bei der gewöhnlichen Polymerisation in wäßriger Suspension geschieht. Das nach der Erfindung hergestellte Copolymerisat zeichnet sich dadurch aus, daß sich in dem Polypropylen-Pfropfcopolymerisat aus nahezu kugelförmigen Teilchen die Pfropfäste nicht nur auf der Teilchenoberfläche, sondern auch - bedingt durch die Quellung - in den Polypropylen-Teilchen befinden.The shape of the polypropylene particles and the viscosity of the suspension remain practically unchanged during the polymerization. The polymerization mixture obtained is cooled after the polymerization and then further treated in the same manner as in the case of the usual polymerization in aqueous suspension. The copolymer prepared according to the invention is characterized in that in the Polypropylene graft copolymer made from almost spherical particles, the graft branches not only on the particle surface, but also - due to the swelling - in the polypropylene particles.

Durch Verwendung eines geeigneten Lösungsmittels zum Quellen lassen sich somit durchweg höhere Pfropfgrade erzielen als bei Pfropfpolymerisationen ohne Lösungsmittel (vgl. Tabelle 1 im Anhang).By using a suitable solvent for swelling, higher degrees of grafting can be achieved than in the case of graft polymerizations without solvents (see Table 1 in the Appendix).

Die pclar-modifizierten Polypropylen-Teilchen eignen sich besonders als Zusatz (ca. 1 bis 50 Gew.-%, vorzugsweise 3 bis 20 Gew.-%, bezogen auf Gesamtmischung) zu Glasfaser- und Füllstoff-haltigem Polypropylen, wodurch eine bessere Haftung zwischen Füllstoff bzw. Glasfaser und Matrix erzielt wird. Solchermaßen modifizierte Polypropylen-Compounds besitzen im Vergleich zu unmodifizierten Polypropylen-Compounds eine wesentlich höhere Biegefestigkeit und Schlagzähigkeit. Weiterhin bewirken Zusätze von polarmodifiziertem Polypropylen zu unmodifiziertem Polypropylen eine bessere Lackierfähigkeit und Bedruckbarkeit. Zusätze von polarmodifiziertem Polypropylen verbessern in Abmischungen von Polypropylen mit polaren Kautschuken wie EthylenVinylacetat-Copolymerisaten, Acrylat-Kautschuken, Acrylnitril-Butadien-Kautschuken u.a. die Ankoppelung Polypropylen/Kautschuk.The pclar-modified polypropylene particles are particularly suitable as an additive (approx. 1 to 50 wt.%, Preferably 3 to 20 wt Filler or glass fiber and matrix is achieved. Polypropylene compounds modified in this way have a significantly higher flexural strength and impact resistance than unmodified polypropylene compounds. Furthermore, additions of polar-modified polypropylene to unmodified polypropylene result in better paintability and printability. Additions of polar-modified polypropylene improve blends of polypropylene with polar rubbers such as ethylene-vinyl acetate copolymers, acrylate rubbers, acrylonitrile-butadiene rubbers and others. coupling polypropylene / rubber.

Die in den Beispielen angegebenen Teile und Prozente beziehen sich auf das Gewicht, sofern nicht anders vermerkt. PP bedeutet Polypropylen.The parts and percentages given in the examples relate to the weight, unless stated otherwise. PP means polypropylene.

Beispiel 1example 1

zu 300 ml Wasser, versetzt mit 1,5 g Emulgator, werden 100 g Polypropylen-Pulver, das zuvor mit 10 Teilen n-Butylacrylat, 30 Teilen Chlorbenzol und 0,5 g Benzoylperoxid homogen vermischt wurde, unter Rühren und Stickstoffüberleitung gegeben. Die Suspension wird zwei Stunden bei 60°C und 4 Stunden bei 90 -95°C gerührt. Nach dem Abkühlen wird das gepfropfte Polypropylen-Pulver abgesaugt, mit Ethanol gewaschen und bei 60°C im Wasserstrahlvakuum getrocknet. Das erhaltene Pfropfpolymerisat ähnelt im Aussehen dem eingesetzten Polypropylen. Es besitzt auch das gleiche Schüttverhalten. Die Menge an n-Butylacrylat auf dem Polypropylen läßt sich IR-spektroskopisch oder mittels Sauerstoff-Analyse bestimmen. Pfropfgrad: 48 %.to 300 ml of water, mixed with 1.5 g of emulsifier, 100 g of polypropylene powder, which was previously mixed homogeneously with 10 parts of n-butyl acrylate, 30 parts of chlorobenzene and 0.5 g of benzoyl peroxide, are added with stirring and a nitrogen blanket. The suspension is stirred for two hours at 60 ° C and 4 hours at 90-95 ° C. After cooling, the grafted polypropylene powder is suctioned off, washed with ethanol and dried at 60 ° C. in a water jet vacuum. The resulting graft polymer resembles the polypropylene used. It also has the same bulk behavior. The amount of n-butyl acrylate on the polypropylene can be determined by IR spectroscopy or by means of oxygen analysis. Degree of grafting: 48%.

Beispiel 2Example 2

Wie Beispiel 1, jedoch werden anstelle von 10 Teilen n-Butylacrylat 10 Teile t-Butylacrylat eingesetzt. Pfropfgrad: 39 %.Like example 1, but instead of 10 parts of n-butyl acrylate, 10 parts of t-butyl acrylate are used. Degree of grafting: 39%.

Beispiel 3Example 3

Wie Beispiel 1, jedoch werden anstelle von n-Butylacrylat 10 Teile Acrylsäure eingesetzt. Pfropfgrad: 96%.Like example 1, but 10 parts of acrylic acid are used instead of n-butyl acrylate. Degree of grafting: 96%.

Beispiel 4Example 4

Wie Beispiel 1, jedoch wird anstelle eines Polypropylen-Homopolymerisats ein pulverförmiges Polypropylencopolymerisat, das ca. 3 Gew.-% Ethylen in Form von Blöcken copolymerisiert enthält, eingesetzt. Pfropfgrad 47 %.Like example 1, but instead of a polypropylene homopolymer, a powdered polypropylene copolymer containing about 3% by weight of copolymerized ethylene in the form of blocks. Degree of grafting 47%.

Beispiel 5Example 5

Wie Beispiel 4, jedoch werden anstelle von 10 Teilen n-Butylacrylat 10 Teile Acrylsäure eingesetzt. Pfropfgrad 93 %.Like example 4, but instead of 10 parts of n-butyl acrylate, 10 parts of acrylic acid are used. Degree of grafting 93%.

Beispiel 6Example 6

Wie Beispiel 1, jedoch werden anstelle von 10 Teilen n-Butylacrylat und 30 Teilen Chlorbenzol 2 Teile Methacrylsäure und 10 Teile Chlorbenzol eingesetzt. Pfropfgrad 19 %.As in Example 1, but instead of 10 parts of n-butyl acrylate and 30 parts of chlorobenzene, 2 parts of methacrylic acid and 10 parts of chlorobenzene are used. Degree of grafting 19%.

Beispiel 7Example 7

In Tabelle 1 sind Polypropylenpfropfcopolymerisate zusammengestellt, die in Abwesenheit bzw. in Gegenwart eines Quellungslösungsmittels hergestellt wurden, und zwar gemäß den Bedingungen des Beispiels 1. Die in Gegenwart von Chlorbenzol als Quellungslösungsmittel hergestellten Pfropfcopolymerisate weisen stets höhere Pfropfgrade auf als entsprechende Pfropfpolymerisate, die ohne Quellungslösungsmittel hergestellt wurden.Table 1 lists polypropylene graft copolymers which were prepared in the absence or in the presence of a swelling solvent, in accordance with the conditions of Example 1. The graft copolymers prepared in the presence of chlorobenzene as swelling solvents always have higher degrees of grafting than corresponding graft polymers which are prepared without swelling solvents were.

Als Vergleich sind auch Pfropfcopolymerisate aufgeführt, die entsprechend der DE-OS 2 640 059 mit Styrol als Quellungsmittel hergestellt worden sind. Sie weisen merklich niedrigere Pfropfgrade auf als solche, die mit Chlorbenzol hergestellt wurden.For comparison, graft copolymers are also listed which, according to DE-OS 2 640 059, contain styrene as Swelling agents have been produced. They have markedly lower degrees of grafting than those made with chlorobenzene.

Die Pfropfgrade wurden ermittelt, indem das Polypropylen-Pfropfcopolymerisat einprozentig in Xylol eine halbe Stunde lang unter Rückfluß erhitzt wurde. Anschließend wird die heiße Lösung in die gleiche Menge kalten Ethylacetats unter Rühren gegeben. Die erhaltene Mischung wird einen Tag bei Raumtemperatur stehengelassen, wobei das Polypropylen-Pfropfcopolymerisat ausfällt. Das ausgefällte Produkt wird abfiltriert, getrocknet und auf nicht gelöste Pfropfanteile (IR-Spektrum, Sauerstoffanalyse) untersucht. Als Pfropfgrad wird das Verhältnis des auf dem Polypropylen nach dem Umfällen verbliebenen Anteils an Pfropfmonomer zu dem vor dem Umfällen ermittelten definiert.The degrees of grafting were determined by heating the polypropylene graft copolymer one percent in xylene under reflux for half an hour. The hot solution is then added to the same amount of cold ethyl acetate with stirring. The mixture obtained is left to stand at room temperature for one day, during which the polypropylene graft copolymer precipitates. The precipitated product is filtered off, dried and examined for undissolved graft components (IR spectrum, oxygen analysis). The degree of grafting is defined as the ratio of the proportion of grafting monomer remaining on the polypropylene after the repeating to that determined before the repeating.

Beispiel 8Example 8

In der Tabelle 2 sind ausgewählte mechanische Eigenschaften von Glasfaser-verstärkten Polypropylen-Compounds gegenübergestellt. Die mit Acrylsäure gepfropftem PP versetzten Compounds besitzen ein deutlich höheres Eigenschaftsniveau als ein Compound mit ungepfropftem Polypropylen (Compounds 2 und 3 im Vergleich zu Compound 1). Vergleicht man jedoch die Compounds 2 und 3 untereinander, die beide 10 Tle.Table 2 shows selected mechanical properties of glass fiber reinforced polypropylene compounds. The compounds grafted with acrylic acid PP have a significantly higher property level than a compound with ungrafted polypropylene (compounds 2 and 3 compared to compound 1). However, if you compare Compounds 2 and 3 with each other, both 10 parts.

Acrylsäure-gepfropftes Polypropylen enthalten, so besitzt Compound 3 eine wesentlich höhere Festigkeit und Kerbschlagzähigkeit als Compound 2. Compound 3 enthält ein Acrylsäure-gepfropftes Polypropylen, das mit einem Zusatz an organischem Lösungsmittel gepfropft wurde, während Compound 2 Acrylsäure-gepfropftes Polypropylen enthält, das ohne Zusatz eines organischen Lösungsmittels gepfropft worden ist.Containing acrylic acid-grafted polypropylene, Compound 3 has a much higher strength and Impact Strength as Compound 2. Compound 3 contains an acrylic acid-grafted polypropylene that has been grafted with an addition of organic solvent, while Compound 2 contains acrylic acid-grafted polypropylene that has been grafted without the addition of an organic solvent.

Das für Compound 2 (Vergleichsbeispiel) verwendete, ohne Zusatz eines organischen Lösungsmittels gepfropfte Polypropylen entspricht dem Pfropfcopolymerisat des Tests 3 aus Tabelle 1 und das für Compound 3 (Beispiel gemäß Erfindung) eingesetzte, in Gegenwart von Chlorbenzol gepfropfte Polypropylen dem Pfropfcopolymerisat des Tests 4 aus Tabelle 1.

Figure imgb0001
Figure imgb0002
 The polypropylene used for compound 2 (comparative example) and grafted without the addition of an organic solvent corresponds to the graft copolymer of test 3 from table 1 and the polypropylene used for compound 3 (example according to the invention), grafted in the presence of chlorobenzene, corresponds to the graft copolymer of test 4 from table 1.
Figure imgb0001
Figure imgb0002

Claims (5)

1) Verfahren zur Herstellung von modifizierten Polypropylen-Teilchen durch Polymerisation von Vinylmonomeren in wäßriger Suspension, wobei a) eine wäßrige Suspension hergestellt wird, die auf 100 bis 2000 Gew.-Tle. Wasser 100 Gew.-Tle. Polypropylen-Teilchen, 4-30 Gew.-Tle. eines Vinylmonomeren, und - auf 100 Gew.-Tle. des Monomeren bezogen - 0,1-10 Gew.-Tle. eines Radikalkettenpolymerisationsinitiators enthält, der bei einer Temperatur von 80-135°C eine Halbwertszeit von mindestens 2 h aufweist, b) die wäßrige Suspension ohne Zersetzung des Initiators erwärmt wird, wobei das Polypropylen angequollen wird und das Monomere in das Polypropylen eindringt, und anschließend c) die wäßrige Suspension so lange auf Temperaturen %85°C gehalten wird, bis die Polymerisation des Monomeren abgeschlossen ist, dadurch gekennzeichnet, daß das Vinylmonomere ein polares Vinylmoneres ist und die wäßrige Suspension zusätzlich 30-120 Gew.-Tle, bezogen auf 100 Gew.-Tle des Monomeren, eines organischen Lösungsmittels enthält, das in der Lage ist, Polypropylen anzuquellen, dessen Siedepunkt bei 760 Torr mindestens 100°C beträgt und das mit den Monomeren in beliebigen Verhältnissen mischbar ist. 1) Process for the preparation of modified polypropylene particles by polymerization of vinyl monomers in aqueous suspension, wherein a) an aqueous suspension is prepared, the 100 to 2000 parts by weight. Water 100 parts by weight Polypropylene particles, 4-30 parts by weight. of a vinyl monomer, and - to 100 parts by weight. of the monomer - 0.1-10 parts by weight. a radical polymerization initiator which has a half-life of at least 2 hours at a temperature of 80-135 ° C, b) the aqueous suspension is heated without decomposition of the initiator, the polypropylene being swollen and the monomer penetrating into the polypropylene, and then c) the aqueous suspension is kept at temperatures% 85 ° C until the polymerization of the monomer is complete, characterized in that the vinyl monomer is a polar vinyl monomer and the aqueous suspension additionally 30-120 parts by weight, based on 100 Parts by weight of the monomer, an organic solvent capable of swelling polypropylene, the Boiling point at 760 Torr is at least 100 ° C and is miscible with the monomers in any ratio. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Vinylmonomere C1-C7-Alkylacrylate, C1-C7-Alkylmethacrylate, (Meth)Acrylnitril, (Meth)Acrylamid, Acrylsäure, Methacrylsäure, Glycidyl(meth)acrylat, δ-(Meth)-Acryloyloxypropyltrimethoxy-silan, Maleinsäureanhydrid oder deren Mischungen verwendet werden.2) Method according to claim 1, characterized in that as vinyl monomers C 1 -C 7 alkyl acrylates, C 1 -C 7 alkyl methacrylates, (meth) acrylonitrile, (meth) acrylamide, acrylic acid, methacrylic acid, glycidyl (meth) acrylate, δ - (Meth) -Acryloyloxypropyltrimethoxysilane, maleic anhydride or mixtures thereof can be used. 3) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Lösungsmittel aromatische Kohlenwasserstoffe, aliphatische Kohlenwasserstoffe und halogenierte aromatische Kohlenwasserstoffe verwendet werden.3) Method according to claim 1, characterized in that aromatic hydrocarbons, aliphatic hydrocarbons and halogenated aromatic hydrocarbons are used as solvents. 4) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Lösungsmittel Chlorbenzol, Dichlorbenzol, Toluol oder Xylol oder ein Gemisch dieser Lösungsmittel verwendet wird.4) Method according to claim 1, characterized in that chlorobenzene, dichlorobenzene, toluene or xylene or a mixture of these solvents is used as the solvent. 5) Verwendung der gemäß Anspruch 1 erhaltenen polarmodifizierten Polypropylenteilchen als Zusatz zu nichtmodifiziertem Polypropylen oder nichtmodifiziertem, glasfaserverstärktem Polypropylen in Mengen von 1 bis 50 Gew.-%, bezogen auf Gesamtmischung.5) Use of the polar-modified polypropylene particles obtained according to claim 1 as an additive to unmodified polypropylene or unmodified, glass fiber-reinforced polypropylene in amounts of 1 to 50% by weight, based on the total mixture.
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CN110358012B (en) * 2018-04-10 2021-09-21 中国石油化工股份有限公司 Method for grafting water-insoluble monomer by propylene polymer aqueous suspension

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EP0239685A1 (en) * 1984-10-04 1987-10-07 Hercules Incorporated N-Alkyl methacrylate modified polypropylene
EP0184321A2 (en) * 1984-11-05 1986-06-11 Sumitomo Chemical Company, Limited Composition of a polypropylene and an ethylene copolymer
EP0184321A3 (en) * 1984-11-05 1988-03-30 Sumitomo Chemical Company, Limited Composition of a polypropylene and an ethylene copolymer
EP0183493A2 (en) * 1984-11-22 1986-06-04 Mitsui Petrochemical Industries, Ltd. Modified ethylenic random copolymer
EP0183493A3 (en) * 1984-11-22 1987-05-20 Mitsui Petrochemical Industries, Ltd. Modified ethylenic random copolymer
EP0295821A3 (en) * 1987-06-16 1991-07-03 Nippon Oil And Fats Company, Limited Method for production of graft resin composition
EP0295821A2 (en) * 1987-06-16 1988-12-21 Nippon Oil And Fats Company, Limited Method for production of graft resin composition
EP0340566A2 (en) * 1988-05-02 1989-11-08 General Electric Company Reactive graft polymers
EP0340566A3 (en) * 1988-05-02 1991-07-03 General Electric Company Reactive graft polymers
US5523358A (en) * 1988-11-21 1996-06-04 Mitsui Petrochemical Industries, Ltd. Modified polyolefin particles and process for preparation thereof
EP0389135A2 (en) * 1989-03-07 1990-09-26 Dsm Copolymer, Inc. Thermoplastic molding composition and molded articles with enhanced surface coating susceptibility
EP0389135A3 (en) * 1989-03-07 1991-12-18 Dsm Copolymer, Inc. Thermoplastic molding composition and molded articles with enhanced surface coating susceptibility
DE4319103C2 (en) * 1993-06-04 2001-04-05 Inst Polymerforschung Dresden Process for the production of polar modified polypropylene filaments
EP0632071A2 (en) * 1993-07-02 1995-01-04 Rohm And Haas Company Process for preparing segmented copolymers
EP0632071A3 (en) * 1993-07-02 1998-02-25 Rohm And Haas Company Process for preparing segmented copolymers
CN102060961A (en) * 2010-12-09 2011-05-18 南京工业大学 Method for preparing high-density polyethylene-maleic anhydride grafted copolymer by adopting suspension method
CN102060961B (en) * 2010-12-09 2015-04-01 南京工业大学 Method for preparing high-density polyethylene-maleic anhydride grafted copolymer by adopting suspension method

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